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EP0735008B1 - Emulsionen auf Basis von Acrylpolymeren - Google Patents

Emulsionen auf Basis von Acrylpolymeren Download PDF

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Publication number
EP0735008B1
EP0735008B1 EP96104483A EP96104483A EP0735008B1 EP 0735008 B1 EP0735008 B1 EP 0735008B1 EP 96104483 A EP96104483 A EP 96104483A EP 96104483 A EP96104483 A EP 96104483A EP 0735008 B1 EP0735008 B1 EP 0735008B1
Authority
EP
European Patent Office
Prior art keywords
weight
parts
scanning
butylmethacrylate
emulsions according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96104483A
Other languages
English (en)
French (fr)
Other versions
EP0735008A3 (de
EP0735008A2 (de
Inventor
Ivan Fuso Nervini
Massimo Cesana
Daniele Becchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema SRL
Original Assignee
Elf Atochem Italia SRL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elf Atochem Italia SRL filed Critical Elf Atochem Italia SRL
Publication of EP0735008A2 publication Critical patent/EP0735008A2/de
Publication of EP0735008A3 publication Critical patent/EP0735008A3/de
Application granted granted Critical
Publication of EP0735008B1 publication Critical patent/EP0735008B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/18—Luminescent screens
    • H01J29/28—Luminescent screens with protective, conductive or reflective layers

Definitions

  • the present invention relates to emulsions based on acrylic polymers.
  • the emulsions of the invention are suitable for preparing metallized luminescent screens for cathode ray tubes.
  • the invention relates to the use of special emulsions based on acrylic polymers as single layer which can be volatilized by depolymerization without combustion with slight organic residue concurrently with the panel sealing to the CRT funnel (cathode ray tube).
  • Filming methods utilizing solvent-based filming lakes are known, which, when deposited on a humid phosphor layer, produce a thin and continuous film on which a metal layer condenses by sputtering.
  • the aqueous emulsion deposits, which is dried by heating.
  • this polymeric film is to remove the irregular surface of the phosphor particles forming the screen, and to provide a very uniform sublayer on which the sputtered metal then deposits in order to form a surface like a mirror to reflect the screen light.
  • the screen then undergoes a treatment at high temperature from 400-450°C (the so called baked-out) to remove the polymeric film.
  • the gaseous products of the polymeric film decomposition come out of the holes of the metal layer.
  • a drawback of this process consists in that the carbon residues deriving from the film decomposition lead to an insufficient gloss of the screen.
  • Aqueous emulsions based on acrylic polymers capable of forming films for preparing cathode tubes are described in US patent 5,145,511 . It is a process for manufacturing cathode tubes with only one step of film removal deriving from the emulsion concurrently with the sealing of the cathode tube panel.
  • Object of the invention is an aqueous emulsion based on uncured and uncurable acrylic polymers and having filming temperatures between 20 and 40°C during the forming process of the cathode ray tube, having the following composition:
  • the A, B, C and D percentages are intended as starting comonomers utilized in the process for preparing the emulsion.
  • component A) instead of butylmethacrylate, lauroyl-, decyl-, undecyl-, ethyl-, propyl-, ethylhexylmethacrylate, etc., can for instance be used.
  • component C) instead of methacrylic acid, other polymerizable carboxylic acids, such as acrylic acid, itaconic acid, etc. can be used.
  • methylacrylate can be used considering the relative molecular weight and the different filming temperature of the polymers containing this comonomer.
  • the ratio between the component A) and B) must be such as to give a minimum filming temperature between about 20 and 40°C.
  • the aqueous emulsion object of the patent gives linear uncured and uncurable polymers during the thermal cycle, as defined below, to which the film is subjected during the application leading to the CRT formation, wherefore also under this point of view no carbon residues are produced.
  • the minimum filming temperature (TMF) of the emulsion must be such as to produce the film between about 20 and 40°C with or without the use of coalescent agents.
  • composition of the monomers is such as to produce a higher TMF.
  • DBGA dibutylglycol diacetate
  • coalescent agents are for instance propylene-glycolmonomethylethylether, etc.
  • glass transition temperature (Tg) can be used in the on-set point as filming index.
  • the Tg is generally comprised from 40 to 65°C.
  • the distribution of the particles diameter is of monomodal type, of sizes generally from 100 to 200 nm, excluding coarse particles or particles aggregates leading to a bimodal distribution. Preferably sizes are from 120 to 170 nm.
  • the polydispersion of the particles sizes is narrow, generally lower than 0.1.
  • the weight average molecular weights (Mw) are generally from 100,000 to 500,000 and the distribution of the molecular weights M w/ M n ( M n number average molecular weight) is rather wide, generally from 3.5 to 6.
  • the process for preparing the emulsion of the invention is a conventional process, preferably in semi-batch, which utilizes surfactants and initiators known in the art of emulsions.
  • surfactants sulphonated paraffines, alkylbenzene-sulphonates, nonylphenols ethoxylates, etc., can be mentioned.
  • initiators ammonium, sodium, or potassium-persulphates; tertiary butyl hydroperoxide, cumene hydroperoxide can be mentioned.
  • the final step of the reaction can be formed by a redox treatment to remove the polymerization residues by using the normal catalytic couples, such as for instance sodium formaldehyde sulphoxylate and terbutylhydroperoxide.
  • the normal catalytic couples such as for instance sodium formaldehyde sulphoxylate and terbutylhydroperoxide.
  • the polymers having an acrylic basis obtained from the emulsion are linear and uncured.
  • the properties charateristic of the emulsions of the invention are measurable by means of chemical-physical measurements as reported in Example 1. In particular it is measured the amount of residue at the end of the thermal cycle specified below which simulates that utilized for preparing CRT.
  • thermal cycle carried out in inert ambient, for instance nitrogen is the following:
  • An emulsion having the following composition in % by weight is prepared: Butylmethacrylate (MABU) 50 Methylmethacrylate (MMA) 41 Ethylacrylate (AE) 7 Methacrylic acid (AMA) 2
  • MABU Butylmethacrylate
  • MMA Methylmethacrylate
  • AE Ethylacrylate
  • AMA Methacrylic acid
  • the preemulsifier is washed with 100 kg of demineralized water (pt. 4, Tab. 1); it is cooled, the reaction is completed for one hour at the same temperature. Then the reactor is cooled to 50°C (pt. 5, Tab. 1) and the redox system is added to complete the removal of the residual monomers. The redox mixture is reported in pt. 6, Tab. 1 and the reaction is carried out for 30 minuts. At the end, at the temperature of about 40°C, DBGA (dibutylglycolacetate) is added, 5 parts by weight per 100 parts by weight of the total weight of the A+B+C+D monomers forming the emulsion copolymer.
  • DBGA dibutylglycolacetate
  • a Counter Nanosizer N4MD was utilized with the following modalities.
  • the cuvette Considering the temperature (20°C), viscosity and refraction index parameters of the suspending agent (1.33 of the deionized water), the cuvette is positioned in the proper place and it is let thermostate for about 10 minutes.
  • the other tests for determining the glass transition, the organic residue, the distribution of the molecular weights, are not carried out on the emulsion but on the dried product working as follows.
  • the emulsion is poured into an aluminium support having a diameter of 5 cm and depth of 0.7 cm, so that the thickness is of about 2-3 mm, it is put in stove at 70°C for 12 hours to dry the product.
  • a film having an 1.5 mm thickness adhering to the support is obtained.
  • the film is punched to obtain disks having a diameter of about 4 mm.
  • a DSC (differential scanning calorimeter) of Mettler TA30 type was utilized. About 20-30 mg of product in the form of a disk, obtained as above, are introduced in the proper aluminium container, whose lid is pierced. The sample is heated at the rate of 20°C per min. starting from -100°C up to 100°C. The test is carried out at least twice on different samples until the onset Tg has a maximum variation within 2°C, preferably 1°C. Also the mid-point and end-set Tg were measured.
  • thermobalance Mettler M3 was utilized. The thermogravimetric analysis is carried out on 20 mg of product in the form of a disk, prepared as above. The disk is loaded into an alumina pot, the pot is then introduced in the thermobalance stove. A nitrogen flow (20 liters/hour) is maintained in the stove; before starting heating one awaits 20 minutes so as to allow the complete removal of the oxygen present in the room. After this period heating is started according to the following thermal profile
  • An equipment Waters 510 is utilized and it is operated as follows. About 80 mg of product in the form of a disk are dissolved in 4 cm 2 of CHCl 3 . The so obtained solution is injected into a liquid chromatograph.
  • Ultrastyragel columns 10 6 10 5 10 4 10 3 (polystyrene cured with divinylbenzol). Refraction index detector, mobile step CHCl 3 , calibration with polystyrene. The data of the characterization indicated above are reported in Table 2. The minimum filming temperature (TMF) was determined according to ASTM D2354 standard.
  • the emulsion is prepared according to the procedure of Example 1 but using the following composition in % by weight: Butylmethacrylate (MABU) 65.3 Methylmethacrylate (MMA) 25.7 Ethylacrylate (AE) 7 Methacrylic acid (AMA) 2. Moreover after point 6 of Example 1 no coalescent is added. The characterization data are reported in Table 2.
  • the emulsion is prepared according to the procedure of Example 1 but using the following composition in % by weight: Butylmethacrylate (MABU) 30 Methylmethacrylate (MMA) 61 Ethylacrylate (AE) 7 Methacrylic acid (AMA) 2. According to the procedure of Example 1, 6 parts by weight of dibutylglycolacetate (DBGA) coalescent on the total weight of the monomers introduced as specified above, are added. The characterization is reported in Table 2.
  • MABU Butylmethacrylate
  • MMA Methylmethacrylate
  • AE Methylacrylate
  • AMA Methacrylic acid
  • An emulsion was prepared by mixing the two emulsions of Example 4 and 5 in volume ratio 1:1.
  • the organic residue remaining after the thermal cycle indicated is of the same order as in Example 4.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)
  • Paints Or Removers (AREA)

Claims (8)

  1. Verwendung von wässrigen Emulsionen auf Basis von ungehärteten und nicht härtbaren Acryl-Polymeren während des Bildungsverfahrens für eine Kathodenstrahlröhre, umfassend als Comonomere die folgenden Komponenten:
    A) Butylmethacrylat 45-70 Gewichtsteile
    B) Methylmethacrylat 20-45 Gewichtsteile
    C) Methacrylsäure 1 - 4 Gewichtsteile
    D) Ethylacrylat 5 - 9 Gewichtsteile
    mit einer solchen minimalen Filmbildungstemperatur, daß Filme zwischen etwa 20 und 40°C gebildet werden, mit oder ohne die Verwendung von koaleszierenden Mitteln, wobei der thermische Stickstoff-Zyklus, der während des KSR-Verfahrens eingesetzt wird, wie folgt ist:
    1. Scannen:
    25°C bis 375°C bei 11°C/Min.
    2. Scannen:
    375°C bis 440°C bei 5°C/Min.
    3. Scannen:
    isotherm bei 440°C für 45 Minuten,
    wobei der organische Rückstand nach der thermischen Behandlung geringer als 0,05 Gew.-% ist.
  2. Verwendung der Emulsionen nach Anspruch 1, bei welcher als Komponente A) anstelle von Butylmethacrlyat Lauroyl-, Decyl-, Undecyl-, Ethyl-, Propyl-, Ethylhexylmethacrylat eingesetzt wird; als Komponente C) anstelle von Methacrylsäure andere polymerisierbare Carbonsäuren wie beispielsweise Acrylsäure, Itaconsäure verwendet werden.
  3. Verwendung der Emulsionen nach Anspruch 1 oder 2, bei welcher als D) Methylacrylat verwendet wird.
  4. Verwendung der Emulsionen nach den Ansprüchen 1-3, bei welcher 3-7 Gew.-% eines koaleszierenden Mittels zugesetzt werden.
  5. Wässrige Emulsionen auf der Basis von ungehärteten und nicht härtbaren Acryl-Polymeren während des Bildungsverfahrens für eine Kathodenstrahlröhre, umfassend als Comonomere die folgenden Komponenten:
    A) Butylmethacrylat 45-70 Gewichtsteile
    B) Methylmethacrylat 20-45 Gewichtsteile
    C) Methacrylsäure 1 - 4 Gewichtsteile
    D) Ethylacrylat 5 - 9 Gewichtsteile
    mit einer solchen minimalen Filmbildungstemperatur, daß Filme zwischen etwa 20 und 40°C hergestellt werden, mit oder ohne die Verwendung von koaleszierenden Mitteln, wobei der thermische Stickstoff-Zyklus, der in dem KSR-Verfahren eingesetzt wird, wie folgt ist:
    1. Scannen:
    25°C bis 375°C bei 11 °C/Min.
    2. Scannen:
    375°C bis 440°C bei 5°C/Min.
    3. Scannen:
    isotherm bei 440°C für 45 Minuten,
    wobei der organische Rückstand nach der thermischen Behandlung geringer als 0,05 Gew.-% ist.
  6. Emulsionen nach Anspruch 5, in welchen als Komponente A) anstelle von Butylmethacrylat Lauroyl-, Decyl-, Undecyl-, Ethyl-, Propyl-, Ethylhexylmethacrylat eingesetzt wird; als Komponente C) anstelle von Methacrylsäure andere polymerisierbare Carbonsäuren wie Acrylsäure, Itaconsäure verwendet werden.
  7. Emulsionen nach den Ansprüchen 5-6, in denen als D) Methylacrylat verwendet wird.
  8. Emulsionen nach den Ansprüchen 5-7, in denen 3-7 Gew.-% eines koaleszierenden Mittels zugesetzt sind.
EP96104483A 1995-03-31 1996-03-21 Emulsionen auf Basis von Acrylpolymeren Expired - Lifetime EP0735008B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI950645 1995-03-31
IT95MI000645A IT1275994B1 (it) 1995-03-31 1995-03-31 Emulsioni a base di polimeri acrilici

Publications (3)

Publication Number Publication Date
EP0735008A2 EP0735008A2 (de) 1996-10-02
EP0735008A3 EP0735008A3 (de) 1997-04-16
EP0735008B1 true EP0735008B1 (de) 1999-07-07

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96104483A Expired - Lifetime EP0735008B1 (de) 1995-03-31 1996-03-21 Emulsionen auf Basis von Acrylpolymeren

Country Status (5)

Country Link
US (1) US5731378A (de)
EP (1) EP0735008B1 (de)
DE (1) DE69603109T2 (de)
IT (1) IT1275994B1 (de)
PL (1) PL184301B1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1275993B1 (it) * 1995-03-31 1997-10-24 Atochem Elf Italia Emulsioni a base di polimeri acrilici
FR2746959A1 (fr) * 1996-04-01 1997-10-03 Rohm & Haas France Procede de fabrication d'un ecran luminescent
AU2110199A (en) * 1998-01-09 1999-07-26 Metabolix, Inc. Polymer compositions providing low residue levels and methods of use thereof
IT1320097B1 (it) * 2000-11-23 2003-11-18 Atofina Dispersioni acquose di polimeri acrilici.

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3067055A (en) * 1959-08-05 1962-12-04 Rca Corp Metallized phosphor screens and method of making same
US3370050A (en) * 1964-06-10 1968-02-20 Pittsburgh Plate Glass Co Preparation of interpolymers of hydroxyl-containing monomers in an organic solvent using hydrogen plroxide as catalyst
US3635867A (en) * 1967-12-05 1972-01-18 Celanese Coatings Co Polymerization process for making aqueous acrylic-containing emulsions
IT1015549B (it) * 1973-07-03 1977-05-20 Vianova Kunstharz Ag Procedimento per la preparazione di dispersioni acquose di polime ri reticolabili e prodotto termoin durente per rivestimenti ottenibile con esse
JPS533053A (en) * 1976-06-30 1978-01-12 Hitachi Ltd Fluorescent reflection surface formation method
JPS5480669A (en) * 1977-12-09 1979-06-27 Sony Corp Manufacture for cathode ray tube and ventilation unit used for its sintering process
JPS5498565A (en) * 1978-01-23 1979-08-03 Hitachi Ltd Manufacture for color receiving tube
US4339475A (en) * 1979-03-23 1982-07-13 Hitachi, Ltd. Method of forming a fluorescent screen for cathode-ray tube
JPS56162451A (en) * 1980-05-19 1981-12-14 Hitachi Ltd Manufacture of color-picture tube and its device
US4327123A (en) * 1981-02-20 1982-04-27 Rca Corporation Method of metallizing a phosphor screen
JPS6071670A (ja) * 1983-09-28 1985-04-23 Hitachi Ltd 陰極線管用フイルミング乳剤
US4600755A (en) * 1985-04-03 1986-07-15 Ppg Industries, Inc. Free radical initiated polymerization of polymerizable ethylenically unsaturated monomer component in the presence of hydrogen peroxide
JPH0749561B2 (ja) * 1988-05-13 1995-05-31 関西ペイント株式会社 水性塗料及びそれを用いる塗装法
JP2983585B2 (ja) * 1990-07-19 1999-11-29 三菱レイヨン株式会社 Ｃｒｔアルミバック用アンダーコート被膜の形成方法
US5216065A (en) * 1990-11-29 1993-06-01 The Mead Corporation Emulsion polymerization with large particle size
JP3128005B2 (ja) * 1991-04-10 2001-01-29 ジェイエスアール株式会社 水性共重合体ラテックス
US5145511A (en) * 1991-11-08 1992-09-08 Videocolor Spa Method for manufacturing a metallized luminescent screen for a cathode-ray tube

Also Published As

Publication number Publication date
PL184301B1 (pl) 2002-09-30
ITMI950645A0 (it) 1995-03-31
ITMI950645A1 (it) 1996-10-01
EP0735008A3 (de) 1997-04-16
IT1275994B1 (it) 1997-10-24
DE69603109D1 (de) 1999-08-12
DE69603109T2 (de) 1999-10-28
PL313554A1 (en) 1996-10-14
US5731378A (en) 1998-03-24
EP0735008A2 (de) 1996-10-02

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